Primary gas- and particle-phase emissions and secondary organic aerosol production from gasoline and diesel off-road engines.

Dilution and smog chamber experiments were performed to characterize the primary emissions and secondary organic aerosol (SOA) formation from gasoline and diesel small off-road engines (SOREs). These engines are high emitters of primary gas- and particle-phase pollutants relative to their fuel consumption. Two- and 4-stroke gasoline SOREs emit much more (up to 3 orders of magnitude more) nonmethane organic gases (NMOGs), primary PM and organic carbon than newer on-road gasoline vehicles (per kg of fuel burned). The primary emissions from a diesel transportation refrigeration unit were similar to those of older, uncontrolled diesel engines used in on-road vehicles (e.g., premodel year 2007 heavy-duty diesel trucks). Two-strokes emitted the largest fractional (and absolute) amount of SOA precursors compared to diesel and 4-stroke gasoline SOREs; however, 35-80% of the NMOG emissions from the engines could not be speciated using traditional gas chromatography or high-performance liquid chromatography. After 3 h of photo-oxidation in a smog chamber, dilute emissions from both 2- and 4-stroke gasoline SOREs produced large amounts of semivolatile SOA. The effective SOA yield (defined as the ratio of SOA mass to estimated mass of reacted precursors) was 2-4% for 2- and 4-stroke SOREs, which is comparable to yields from dilute exhaust from older passenger cars and unburned gasoline. This suggests that much of the SOA production was due to unburned fuel and/or lubrication oil. The total PM contribution of different mobile source categories to the ambient PM burden was calculated by combining primary emission, SOA production and fuel consumption data. Relative to their fuel consumption, SOREs are disproportionately high total PM sources; however, the vastly greater fuel consumption of on-road vehicles renders them (on-road vehicles) the dominant mobile source of ambient PM in the Los Angeles area.

Dicarbonyl products of the OH radical-initiated reaction of a series of aromatic hydrocarbons.

Aromatic hydrocarbons are important constituents of vehicle exhaust and of nonmethane organic compounds in ambient urban air. We used a derivatization technique with methane positive chemical ionization gas chromatography/mass spectrometry to investigate the carbonyl products formed from the OH radical-initiated reactions of toluene, the xylenes, and the trimethylbenzenes. Characteristic diderivatized molecular ions of dicarbonyl products were obtained. Consistent with previous studies, the 1,2-dicarbonyls glyoxal, methylglyoxal, and biacetyl were observed, as were all but one of the possible unsaturated 1,4-dicarbonyl coproducts. Unsaturated 1,4-diketones had formation yields similar to their potential coproduct 1,2-dicarbonyls. However, apart from HC(O)CH=CHCHO, unsaturated 1,4-dialdehydes and keto-aldehydes were generally observed in lower yield than their potential 1,2-dicarbonyl coproducts.